Fiberizable glass compositions



'1 v smart; .FIBERIZABLE GLASS COMPOSITIONS Ralph L. Tiede, Newark,Ohio, assignor, by mesne assignments, to the United States of America asrepresented by the United States Atomic Energy Commission No Drawing.Filed Mar. 15, 1960, Ser. No. 15,072

i '42 Claims. (Cyrus-s ,Thisdnventi'on relates to glass compositions andmore specifically to suitablecompositionsfor forming glass.

thonium gidde containing glasscompositions could be usedtorjsuchpunposes, the actual iiberizable glass compositionshavebeenprovided now for the first time and are for the firsttime'disclosed' herein. 1 H

.In order for the compositions to be suit-able for use" in high speed'methods, requires that afglass 'melt" be produced either from marbles,cullet or from basic raw materials. *In eit-her' event, a rathersubstantial amount of molten glass is maintained for discharge in linestreams through orifices-inteeders, commonly called bushings, thestreams thenbe-ing attenuated in any of numerous mam ners into the" linefibers desired; Continuous fibers which United. States Patentposit-ionshaving a high proportion of thorium oxide as an essentialingredient.

It a further object to proyide compositions of the silica, soda.thoriasystem which. are fiberizableby. known methods and whichcan be,produced economically and commercially.

Further objects will be apparent-from the many ples and from thedescription which follows.

Glass compositions of the silica, soda, thoria' system whichincludhfrom' about 5-35 by weight thoria are illustrated in the tol-lowing" examples "thatset suitable compositions for the purposes ofthe linvfition.

exam,-

. the production of fibers, they must meet an exacting set I ofstandards. Fiber production, according to present-day are pulled andwound upon a 'colletwinder have been produced from the compositions ofthe present invention. process is well-known to all those skilled in theThe invention herein relates not toprqcess but rather the i e ve 99 m ad rec ro sp cifi glass P s tions w i Provid ene y y yr p zl turerelationships to allow fiberization and also provide the Y desiredphysical properties such 'as durability and strength which have beenfound necessary in compositions which areto bernanuiactured into fibers.r 1 Glass as it is commonly known is-a super-cooled liquid 7 and is notin an equilibrium condition. tAs-ordinary glass is 'heated fromroomtemperaturqit passes through a range of temperatures at which itsoftens, first toa relatively viscous liquid condition. Further heatingof glass above the softening range eventually brings it to a liquidusor; devitrifi-cation temperature. Above the liquidus temperature'the'glass'"eiiists;"under equilibrium conditions, as a liquid. Belowsuch temperature, glass e itists at equilibrium, 'in' a' 'ci'ystal-linesta'te. "At temperaturesju'st' below the liqiiidusfdevitrification occursat a 'rapi'd'rateI Glass to fiber iied' must be melted and mustalsobmaint'ained at '100'or' so above its liduidus in order to prevent'devitrification or even pantia-l devitrificatiqn which might occur in,the. melting. tank or in thewicinity ofthe bushingor feeder. ifja lower.temperature.

e ain ned...

l The range of temperatures product-ionjor fiberization, therefore, isbetween the liquidus" temperature of the glass being .fi-berized and thepermissibleoperating temperature of the feeder. In order I I to besuited for the production of glass fibers by commercial techniques,glass musthave a 'liquidus temperature substantiallylower than themaximum permissible operat ingtemperature of a feeder Whichis'usuallyfrom about;

2500 to about-Z800" F and preferaibly is not higher than about 2.600-F.The :glassmusthave aviscosity suitable forfiberization at a temperatureabove its "liquidus' tern-1 peranire but below perature.

" It is anobject of this'invention "to provide glass 'com'- such maximumbushing operating temg and urin-ia are added. 7

The follo win'g are examples of specific compositions that have beenmelted and'a-re fiberizable by known proc- .esses.

Example-I SiO I 69.93 Al O .07 Na O W 9.99 (F6203 r I .03 Th0 19.98

. Example 11 Si0 Y 59.95 2 3 J06 Na O 19.98 R2 23 3 ThO 19.98

. 40 Example III S'iO i 49.86 A1 0 v .05 Na o a r 9 29.98 Fe' O 1 1 I'IhO 19.99

Bushing operating temperature 28 10? -F. Fiber diameter .00035".

Example IV I v Percent- F Si0 59x95 A1 0 o6 'Na O 9.99 F6203 .03 'IhO29.97

Example V- I SiO l; 49.96 A1 0 l .05 Na O 9,99

: Fe O v .03- IhO M 2.9.98 K 0 9.99,

5. Example VI. j;

.. SiO 1 44.97

Na O I 9.99 Fe o 7 I .0Q' K 0 r Lr; 9.99

T hO r 29.98 V 0 5.00

3,132,033 9 i; "Patented May 5 1964 3 Example VII Percent SiO 49.96 A105 .05 M 7.49 F6203 .03 K 0 7.49 T110 29.98 V 0 5.00

Example VIII 520 44.97 A1 0 .05 Na O 7.49 F6203 .02 K 0 7.49 T-hO 29.98V205 Example IX 7 sio 69.92 A1 0 .07 Na O 19.98 F3203 .04 T1102 9.99

V 4 ExampleX I SiOg 64.94 A1 0 .O7 Na O 24.98 PC2023 .03 ThO T 9.99

7 Example XI SiO 59.95 A1 0 .06 Na O 1 29.97 F6203 .03 ThO 9.99

Bushing Operating temperature 2200 'F.

Fiber diameter .00014.

Example XII V v Percent SiO V 54.95 'Al O 1 .06 Na O 34.97 F6203 .03 ThO9.99

ExampleXlII SiO 64.94

Na O 19.98 Fe O .03 T110 14.99

' ExampleXIV I Si0 59.95 A1 0 .06 Na o 24.98 F8203 'IhO 14.99

. ExampleXV S10 54.95 A1 0 1 .06 Na 0 29.97 R2 0 .03 T110 14.99

Bushing operating temperature 1970 F. Fiber diameter .00016".

. 4 Example XVI Percent SiO "49.96 A1 0 .05 Na o I 34.97 Fe O .03 T v14.99

Example XVII SiO 49.97 A1203 Na O 34.98 Fezo'g 2 5.00 T110 14.99

- Example XVIII SiO 49.97 A1 0 .05 Na O g 29.98 F6203 l I .02 T110 19.99F2 Bushing operating temperature 1700 Fiber diameter .00016.

Example XIX i Percent SiO 47.33 A1 0 .05 Na O 7.89 F203 .02 K 0 7.89 ThO26.30 V 0 10.52

. Example XX SiO 47.59 A1203 v Na O E 23.79 F203 .02 ThO 23.79 F 4.76

r ExampleXXl 'SiO 47.59 A1 0 .05 Na 'O 19.04

Example XXII SiO 52.34 A1 0 L05 Na O 14.27 F6203 .03 T110 28.55 F 4.76

" Example XXIII SiO V 44.97 A1 0 .05 Na o 5.00 F203 .02 K 0 5.00 T-hO29.98 V 0 14.99 Example XXIV SiO A1 0 .05 Na o 4.76 F6 0 .02 K20 I 4.76ThO 28.55 V205 F 4.76

Example XXV Percent sio 44.97

A1205 .05 Na O 5.00 2 E 2 5% "11 29:98 v.0. 9.99 zno 5.00

T Q Example XXVI sio 44.97,

Na O I??? 5'83 Tiio 29:98 V205 9.99 S1102 5.09

p 7 Example XXVII 7 53.62 A1203? .05 Na' O- 9.75 R 0 .03 T110 I 3 1. 1 2

: Examples III, XI XV and XVIII provided good fibers. V suitable for thepurposes of this invention. Silica, soda and thoria are consideredessential ingredientsin all these compositions. A partial substitutionof potassia for soda can' be made as is illustrated in many of theexamples. It

' has been found that the partial substitution of potassia Example. XXVIII Example XXXII f t Percent s10 1 34.98 A1303 J 0 14.99 U308 2 5 .02T110 9 Example-jXXXlII Y s o 29.99 A1 0 .03 Na o 14.99 0 39.98 2 3 .02ThO Q 14.99

. Example XXXIV SiO 44.97 2 3 .05 N o 14.99 0 19.99 F6203 .02 T110 19.99Example XXX V SiO 24.99 A1 0 .03 N Q 10.00 U 0 39.98 F3203 ThO 19.99 v 05.00

Example XXXVI H SiO 55.95 A1 0 ".06' Na O g 23.98 U 0 9.9 9 F203 .03 ThQ9.99

Bushing operating temperature 2250 F.

Fiber diameter .00012".

. Example XXXVII Percent" SiO 55.95 A1 0 .06 Na O p I 23.9 8 U308 Fego3I I T110 14.99'

Bushing operating temperature 2300 F. Fiber diameterZOOOIS ExampleXXXVIII T Percent SiO 47.59 A1 0 .05 N3 0 14.28 F6203 Th0 33.31 F 4.76

Bushing operating temperature 2200 F. 9 Fiber diameter .00013". f

1 both thoria and urania. in every aspect, it has been foundfithaturania can be Percent Si0 44.97 A1 0 .05. Na O 14.99

I U 0 34.98 F6203 .02, ThO 5.00;

This is a'clear blackglass as are the compositions of Examples XXIX toXXXIIL 1 Example XXIX Percent SiO 44.97. A1 0 '.05 Na O 14.99 U 0 29.98-Fe O .02

" Example XXX .Na O 14.99 .U O 24.98 F6203 1 .02

ThO 14.99-

9 Example XXXI Nago 14.99. U 0 39.98 mo. .02

ThO 5.00

These lattertexamples;withithe exception .of Example XXXVIII, set forthfiberizable compositions comprising Although not equivalent oxides addedto the thoria glass compositions in anelfort to increase the totalradio-active material and. still retain' the .properviscosity-tempreature relationship for fiberizing. I

- Various modifying'oxides can be addedto the compositions but they arenot deemed to be essential. For

instance, vanadia, zirconia, tin oxide, lead oxide, and zinc oxide canbe added. Vanadia allows the addition of high proportions of thoriawhile retaining the proper viscositymas e re a i sh 19. a loy! fiber zaion- .I has also been found thatfluorides can be'added to the glasscomposition. The fluorine can be added in the form of sodinmsilicofiuoridefor suitable material sqch as calcium fluoride and others.7 It was found that an addition of approximately F appearedto be theoptimum proportion. Up to liof thefluorine added islost'dur 1 ent. "Thevast majorityiof these compositions were melted at a temperature of from26502750 F. One eXcep-- tion was'the' composition of Example VIwhich wasmelted at 2850 F. Many of the compositoins disclosed have been found tobe leachable by acid to produce high tem-.

perature resistant glassfibers. I V

t t l v b s i operating em ra u ssand fiber diameters ha ve beenindicated theseare not limits but merely indicative. V t 7 WModifications and variations lwithin the scope of the appended claimsare intended to be included.

I claim: I

1. A glass composition consisting essentially. of by weight, 9.93% SiO.O7% Al Q 9.99% Na O, .03% F6203 T1102! 7 I 2. A glass compositionconsisting essentiallyof by Weight,:59.95% SiO 06% 1 0 19.9 Na O, .03%

3. A glass composition consisting essentiallyof by weight, 49.86% SiO.05% A1 0 29.98% Na O, .02% F6203, and Th02.

4. A glass composition consisting essentiallyof by Weight, .9..95% SiO.06%;Al O ,.9.99% Na O, .03%

5. A glass composition consisting essentially, of by weight, 49.96% SiO.05% A1 0 9.99% Na O, .03% Fe O 29.98% ThO ,'and 9.99% K 0. W I

6. A glass composition consisting essentiallyof by weight, 44.97% SiO.05% A1 0 9.99% Na O, .02% Fe O 9.99% K 0, 29.98% ThO and 5.00% V 0 7. Aglass composition consisting. essentially of by weight, 49.96% SiO- .05%A1 0 7;49% Na O, .03% Fe O 7.49% K 0, 29.98% ThO and 5.00% V 0 8. Aglass composition consisting essentially of by Weight, 39.98% SiO .04%A1 0 7.50% Na O, .02% Fe 0 7.50% K 0, 29.98% ThO and 14.99% V 0 9. Aglass composition consisting essentially of by weight, 69.92% Si0 .07%A1 0 19.98% Na O, .04% Fe O and 9.99% ThO 10. A glass compositionweight, 64.94% SiO .07% Fe O ,'and T1102- 11. A glass compositionweight, 59.95% SiO .06% Fe O and T1102. v

12. A glass composition consisting essentially of by weight, 54.95% SiO.06%.Al O 34.97% Na O, .03% Fe O and 9.99%'ThO 1,3. A glass compositionconsisting essentially of by weight, 64.94% SiO .06% A1 0 19.98% Na O,.O3% Fe O and 14.99% ThO 14. A glass composition weight,59.95% SiO .06%Fe O and 14.99% ThO .v

15. A glass composition weight, 54.95% SiO .06% Fe O and 14.99% ThO 16.A glass composition consisting essentially of by Weight, 49.96% SiO .05%A1 0 34.97% Na O, .03% Fe O and 14.99% T110 17. A glass compositionconsisting essentially of by Al O 24.98% Na O, .03%

consisting essentially of by A1 0 29.97% Na o, .03%

consisting essentially of by A1 0 24.98% Na O, .03%

consisting essentially of by A1 0 29.97% Na O, .03%

consisting essentially of by 8 weight, 49.97% SiO ,".05'% Al O ,34.98%Na O, .02% Fe Q 5.00% F and 14.99% T 18. .A glass composition consistingessentially of by 19. A glass composition consisting essentially of byweight, 47.33% 810 .05% A1 0 7.89% NagO, .02% F6203, T1102, V205.

20. A glass composition consistingessentially of by weight,"47.59%SiO.05% A1 0 23.79% Na O', .02%

21. A glass composition consisting essentially of by Weight, 47.59% SiO.05% A1 0 19.04% Na O, .02% Fe O 28-55% ThO' and 4.76% F 22. A glasscomposition consisting essentially of weight, 52.34% .SiO 05% A1 014.27% Na O, 03% Fe O 28.55%..ThO and 4.76% 1 1 23. A glass compositionconsisting essentially of by weight, 44.97% SiO .05% AI O 5.00% Na O,.02% F'2O3, K20, T1102, and V205.

24. A glass composition consisting essentially of by Weight, 42.83% SiO.05% A1 0 4.76% Na O, .02%

Fe O 4.76% K 0, 28.55% ThO 14.28% V 0 and 25. A lglass compositionconsisting essentially of by l 2 A 2 3,,5- Q N z 4 3. mow- 8% T 02,9.99% no... an 5.00% Zn0. H l H I 26. Ayglass composition consistingessentially of by weight, 44.97% SiO .05% A1 0 5.00% Na O, .02% Fe Of5.00% K 0, 29.98% T110 9.99% V 0 and 5.00% S110 a 27. A glasscomposition consisting essentially of by weight, 53.62% SiO .05% A1 09.75% Na O, .03% Fe Og, 34.12% T110 and 2.44% F 28. Glass compositionconsisting essentially weight, 44.97% SiO 0.05% A1 0 14.99% 34.98% U O,-0.02% Fe O3, and 5.00% ThO 29. Glass com-positionconsistingessentially weight,. 44.97% SiO 0.05% A1 0 14.99%

U303, Fe O 30. Glass composition consisting essentially weigh-t,"44.97%'SiO' 0.05%" A1 0 '14.99%'

of by of by N320,

of by :Na O,

31. Glass composition consisting essentially Weight," 39.98% 'SiO 0.04%A1 0 14.99% 39.98%U Og, 0.02% Fe O and 5.00% ThO .32. Glass compositionconsisting essentially weight, 34.98% SiO 0.04% A1 0 14.99% 39.98% U 00.02% Fe O and 9.99% ThO 33. Glass composition consisting essentiallyweight, 29.99% SiO 0.03% A1 0 14.99% 39.98%. U 0 0.02% Fe O and 14.99%ThO 34. Glass composition consisting essentially weight, 44.97% SiO0.05% A1 0 14.99% 19.99% U O 0.02% 'Fe O and 19.99% T110 35. 'Glasscomposition consisting essentially weight, 24.99% SiO 0.03%. A1 0 10.00%39.98% U 0 0.01%.:Fe O ,,19.99 T110 and V205. N

;36. Glass composition consisting essentially weight, 55.95% SiO 0.06%A1203. 23.98% 9.99% U 0 0.03% Fe o and 9.99% T110 37. Glass composition.consisting essentially weight, 55.95% SiQ 0.06% A1 0 23.98%,

U3O8,U0.03% F6203, 11102.

38. Glass composition consisting essentially weight, 47.59% SiO 0.05% A10 14.28% 0.02% Fe O 33.31% ThO and 4.76% F 39QGlass compositionsuitablefor fiberi'zing comprisof by Na2O,

of by N320,

of by N320,

Nazo, 5.00%

Na2o,

of by a by N320,

percentages being by'weiglit.

ofbyi of by 9 41. Glass compositions comprising 24-56% SiO 10 24% Na O,5-20% 'IhO and a sufiicient quantity of U 0 to increase the radio-activematerial and still retain UNITED STATES PATENTS f 2,199,856 PartridgeMay 7, 1940 Bastick et a1. Aug. 27,1946

Tillyer May 8, 1951 Harteck et a1. "a Mar. 15, 1960 Loewenstein Oct. 23,1962 Tiede Apr. 2, 1963 FOREIGN PATENTS Germany Feb. 14, 1940 GreatBritain Apr. 23, 1958

29. GLASS COMPOSITION CONSISTING ESSENTIALLY OF BY WEIGHT, 44.97% SO2,0.05% AL2O3, 14.99% NA2O, 29.98% U3O8, 0.02% FE2O3, AND 14.99% THO2. 41.GLASS COMPOSITIONS COMPRISING 24-56% SIO2, 1024% NA2O, 5-20% THO2 AND ASUFFICIENT QUANTITY OF U3O8 TO INCREASE THE RADIO-ACTIVE MATERIAL ANDSTILL RETAIN FIBERIZABILITY.